CN107099162A - A kind of RPUI high-performance projects material for sole of shoe - Google Patents
A kind of RPUI high-performance projects material for sole of shoe Download PDFInfo
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- CN107099162A CN107099162A CN201710149875.1A CN201710149875A CN107099162A CN 107099162 A CN107099162 A CN 107099162A CN 201710149875 A CN201710149875 A CN 201710149875A CN 107099162 A CN107099162 A CN 107099162A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/0009—Producing footwear by injection moulding; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D35/00—Producing footwear
- B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
- B29D35/122—Soles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Material for sole of shoe is projected the invention discloses a kind of RPUI high-performance, its formula is as follows：100 parts of sizing material, 0.6 1 parts of bridging agent, 5.2 10.8 parts of auxiliary agent, 25 parts of colorant, and there is provided specific material and prepare application method.The present invention has used the EVA and several elastic composites of high VA contents using RPUI high-performance formula of soles, traditional composite sole (rubber sole+EVA midsoles) Making programme is simplified, rubber-sole on-slip has been had concurrently and wear-resisting and EVA foaming bottoms lightweight and high-elastic characteristic.
Description
Technical field
Present invention relates particularly to a kind of advanced composite material (ACM) used in shoe industry shoe sole production, available for do big bottom,
Midsole.
Background technology
With the development and the continuous progress of scientific level of social economy, people for footwear comfortableness and security often
More requirements are there has also been, are improved constantly such as the requirement to performance the on-slip of footwear, wear-resisting, high-elastic, damping and lighting, footwear
Use classification more refinement, the footwear of various professional purposes are because of different use environments, and the physical property requirement to footwear is also different.Sole stops
Sliding, wear-resisting, lightweight, it is high-elastic be footwear industry development trend.Existing formula of soles can not meet on-slip simultaneously, wear-resisting, lightweight, high-elastic
These requirements；To meet above sole requirement, often using composite sole, such as rubber sole and EVA midsoles or PU midsoles
Combination etc..Elastomeric material on-slip and it is wear-resisting preferably but proportion is high, sole is too heavy；General EVA bottoms are lightweight, but not on-slip, no
It is wear-resisting.To meet high-elastic, on-slip, wear-resisting, lightweight these requirements simultaneously, high-performance formula of soles of the invention can be produced simultaneously
Meet on-slip, wear-resisting, lightweight, high-elastic etc. and require simple sole, and manufacture sole technique can be reduced, save artificial, save
The energy, meets national energy-saving emission reduction policy.
The content of the invention
Material for sole of shoe is projected it is an object of the invention to provide a kind of RPUI high-performance, on-slip is met, wear-resisting, lightweight, high-elastic
Deng requirement, sole is more comfortable durable.The present invention RPUI high-performance project formula of soles production sole simultaneously meet on-slip, it is resistance to
The requirement such as mill, lightweight, high-elastic, improves the comfort level and practical degree of sole, meets the trend of sole development.
A kind of RPUC high-performance moldeds material for sole of shoe, its formula is as follows：
100 parts of sizing material
0.6-1 parts of bridging agent
5.2-10.8 parts of auxiliary agent
2-5 parts of colorant.
The sizing material includes ethylene propylene diene rubber and elastic composite, and the ethylene propylene diene rubber is used
EPDM3722, the elastic composite uses N502 and Infuse 9507.
The formula of the sizing material is as follows：20-50 parts of ethylene propylene diene rubber, 10-30 parts of N502 elastic composites,
30-50 parts of 9507 elastic composites of Infuse.
The bridging agent uses the tasteless peroxide of environment-friendly type, and the peroxide includes but is not limited to Arkema's
Luperox F flakes or AKZO 14S-FC.
The auxiliary agent includes anti-wear agent, stearic acid, alkaline oxygenated zinc and foaming agent, and the auxiliary formula is as follows：Anti-wear agent
2-5 parts, 0.4-0.8 parts of stearic acid, alkaline oxygenated zinc 0.8-2 parts, 2-3 parts of foaming agent.
The anti-wear agent uses DIN150, and the stearic acid uses ST1801, and the alkaline oxygenated zinc uses ZINC, described
Foaming agent uses middle temperature foaming agent, and the middle temperature foaming agent includes but is not limited to South Korea brocade ocean JTR-TL or Lin Gebei HH808B.
Its preparation process is as follows：
Step 1, raw material is weighed according to formula；
Step 2, banbury (also known as profit takes machine) is warming up to 70-80 DEG C, adds micelle and carry out mastication, be continuously heating to
90-100 DEG C, add anti-wear agent, stearic acid, alkaline oxygenated zinc, colorant and kneaded；
Step 3,115-120 DEG C is warming up to, weight mixing is carried out, 100-105 DEG C, input foaming are naturally cooling to during mixing
Agent and bridging agent, continue to knead discharging after 3min, while controlling temperature to be less than 110 DEG C；
Step 4, the kneading material unloaded is put into comminutor and granulated, obtain pellet；
Step 5, the different big small powder of expansion ratio is prepared according to above-mentioned steps, the formulation differences of the small powder and aniseed exist
Foaming agent ratio is 2: 3；
Step 6, aniseed and small powder are loaded into hot pressing ejaculator after expansion ratio ratio is uniformly mixed with batch mixer on demand
Charging basket, then rifle is penetrated by ejaculator inject mould molding, it is described that to penetrate rifle wise temperature parameter as follows：92 DEG C of first paragraph, second segment
92 DEG C, the 3rd section 94 DEG C, the 4th section 94 DEG C；
Step 7, it is put into constant temperature oven after shooting foaming semi-finished product are taken out and makees stable dimensions sizing, constant temperature steadiness parameter：
175℃*500S；
Step 8, constant temperature oven dried after carry out cooling and shaping, cooling condition be 5 DEG C * 5 minutes；
Step 9, repaiied after cooling and shaping except sole flash, you can obtain product shoes bottom.
Granulation conditions in the step 4 are as follows：Set 70 ± 5 DEG C of die head temperature；30 ± 5 DEG C of first paragraph temperature；Second
30 ± 5 DEG C of Duan Wendu；3rd section of 30 ± 5 DEG C of temperature；Set main frame speed 28；Mixer speed 19；Die head motor speed 11 ±
1。
The baking oven time that crosses in the step 7 is 40min, and using five sections of baking ovens, the oven temperature is respectively 75 DEG C/70
℃/65℃/60℃/55℃。
The present invention is heated up with anti-wear agent, alkaline oxygenated zinc and colorant and stirred using the mixing of sizing material, secondly, weight
Added while mixing and put infusion and bridging agent, and granulate obtaining aniseed and small powder；Then aniseed and small powder are mixed equal
Rifle shooting foaming is penetrated in even progress, foamed product is crossed into the stable sizing of baking oven, most afterwards after cooling and shaping, deburring obtains sole.
The present invention is added to sizing material by the way of foaming agent mixing, internal foaming structure can be formed, with foaming
It is uniform, while low-gravity structure, more lightweight can be formed；Frame connection can be carried out while being foamed using bridging agent
Processing, can trigger ethylene propylene diene rubber to carry out crosslinking Treatment, play good structure steady by the high activity of peroxide
Gu effect, with the good askew performance of low pressure contracting；Use based on ethylene propylene diene rubber, shape supplemented by a variety of elastic composites
Into sizing material, the elastomeric property of elastomeric material is made full use of, it is ensured that material for sole of shoe elastomeric property；The present invention uses IP shoot modes
Injection sole is carried out, inside and outside mixed foaming can be carried out, with good foaming effect, while ladder is played in the baking oven sizing after curing
Degree cooling sizing, last quick cooling and shaping, foamed stability is good.
Compared with prior art, the invention has the advantages that：
1st, high resiliency.Vertically bounce-back reaches 50-60% to sole prepared by the present invention, higher than the bounce-back of general sole, comfortableness
It is good.
2nd, good rubber feel, changes the plastic cement feel of common material for sole of shoe.
3rd, lightweight.Material for sole of shoe proportion is 0.38-0.6, and weight is far below General Purpose Rubber bottom.
4th, it is wear-resisting.The wear-resisting 80-150 of DIN, reach the wear-resisting requirement of rubber-sole.
5th, on-slip.Dry/wet on-slip >=0.5/0.3, it is similar with rubber sliding-proof effect.
6th, low pressure contracting is askew.Permanent high compression is askew≤and 40.Sole wears no folding line, indeformable, durable in use.
7th, the preparation method energy-saving and emission-reduction that the present invention is provided.Shoe sole production technique is simple, saves cost of labor, saves energy
Source.
Embodiment
The present invention is described further with reference to embodiment：
Embodiment 1
Big material formula
Small material formula
Its preparation process is as follows：
Step 1, raw material is weighed according to formula；
Step 2, profit, which is taken, is warming up to 70 DEG C in machine, add micelle, be continuously heating to 90 DEG C, add anti-wear agent, stearic acid, alkali
Property zinc oxide, colorant；
Step 3,115 DEG C are warming up to, weight mixing is carried out, 100 DEG C are naturally cooling to during mixing, input foaming agent is with building bridge
Agent, continues to knead discharging after 3min, while controlling 109 DEG C of temperature；
Step 4, the material unloaded is put into comminutor and granulated, obtain pellet；
Step 5, big small powder is prepared according to above-mentioned steps, the formulation differences of the small powder and aniseed are 2 in foaming agent ratio:
3；
Step 6, load after pellet is mixed with small pellets and penetrate rifle and projected, described to penetrate rifle parameter as follows：First paragraph 92
DEG C, 92 DEG C of second segment, the 3rd section 94 DEG C, the 4th section 94 DEG C；
Step 7, shooting foaming is carried out carrying out the stable sizing of baking oven after maturation process, cures parameter：175℃*500S；
Step 8, cross baking oven it is complete after carry out cooling and shaping, cooling condition be 5 DEG C * 5 minutes；
Step 9, deburring after cooling and shaping, you can obtain sole.
Granulation conditions in the step 4 are as follows：Set 65 DEG C of die head temperature；25 DEG C of first paragraph temperature；Second segment temperature
25℃；3rd section of 25 DEG C of temperature；Set main frame speed 28；Mixer speed 19；Die head motor speed 10.
The baking oven time that crosses in the step 7 is 40min, and using five sections of baking ovens, the oven temperature is respectively 75 DEG C/70
℃/65℃/60℃/55℃。
Embodiment 2
Big material formula
Small material formula
Its preparation process is as follows：
Step 1, raw material is weighed according to formula；
Step 2, profit is taken in machine and is warming up to 80 DEG C, adds micelle, is continuously heating to 100 DEG C, add anti-wear agent, stearic acid,
Alkaline oxygenated zinc, colorant；
Step 3,120 DEG C are warming up to, weight mixing is carried out, 105 DEG C are naturally cooling to during mixing, input foaming agent is with building bridge
Agent, continues to knead discharging after 3min, while controlling 103 DEG C of temperature；
Step 4, the material unloaded is put into comminutor and granulated, obtain pellet；
Step 5, big small powder is prepared according to above-mentioned steps, the formulation differences of the small powder and aniseed are 2 in foaming agent ratio:
3；
Step 6, load after aniseed is well mixed with small powder and penetrate rifle and projected, described to penetrate rifle parameter as follows：First paragraph
92 DEG C, 92 DEG C of second segment, the 3rd section 94 DEG C, the 4th section 94 DEG C；
Step 7, shooting foaming is carried out carrying out the stable sizing of baking oven after maturation process, cures parameter：175℃*500S；
Step 8, cross baking oven it is complete after carry out cooling and shaping, cooling condition be 5 DEG C * 5 minutes；
Step 9, deburring after cooling and shaping, you can obtain sole.
Granulation conditions in the step 4 are as follows：Set 75 DEG C of die head temperature；35 DEG C of first paragraph temperature；Second segment temperature
35℃；3rd section of 35 DEG C of temperature；Set main frame speed 28；Mixer speed 19；Die head motor speed 12.
The baking oven time that crosses in the step 7 is 40min, and using five sections of baking ovens, the oven temperature is respectively 75 DEG C/70
℃/65℃/60℃/55℃。
Embodiment 3
Big material formula
Small material formula
Its preparation process is as follows：
Step 1, raw material is weighed according to formula；
Step 2,75 DEG C are warming up in reactor, micelle is added, 95 DEG C are continuously heating to, anti-wear agent, stearic acid, alkali is added
Property zinc oxide, colorant；
Step 3,118 DEG C are warming up to, weight mixing is carried out, 103 DEG C are naturally cooling to during mixing, input foaming agent is with building bridge
Agent, continues to knead discharging after 3min, while controlling 105 DEG C of temperature；
Step 4, the material unloaded is put into comminutor and granulated, obtain pellet；
Step 5, big small powder is prepared according to above-mentioned steps, the formulation differences of the small powder and aniseed are 2 in foaming agent ratio:
3；
Step 6, load after aniseed is well mixed with small powder and penetrate rifle and projected, described to penetrate rifle parameter as follows：First paragraph
92 DEG C, 92 DEG C of second segment, the 3rd section 94 DEG C, the 4th section 94 DEG C；
Step 7, shooting foaming is carried out carrying out the stable sizing of baking oven after maturation process, cures parameter：175℃*500S；
Step 8, baking oven dried after carry out cooling and shaping, cooling condition be 5 DEG C * 5 minutes；
Step 9, deburring after cooling and shaping, you can obtain sole.
Granulation conditions in the step 4 are as follows：Set 70 DEG C of die head temperature；30 DEG C of first paragraph temperature；Second segment temperature
30℃；3rd section of 30 DEG C of temperature；Set main frame speed 28；Mixer speed 19；Die head motor speed 11.
The baking oven time that crosses in the step 7 is 40min, and using five sections of baking ovens, the oven temperature is respectively 75 DEG C/70
℃/65℃/60℃/55℃。
Embodiment 1-3 material is tested
| Detection project | Method of testing | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Vertical bounce-back | VF-B16 | 50% | 53% | 60% | 20-35% |
| Proportion | VF-A04 | 0.6 | 0.57 | 0.38 | 1.1-1.2 |
| DIN is wear-resisting | VF-C01 | 80 | 86 | 150 | 80-150 |
| Dry on-slip | ASTM-1677 | 0.55 | 0.57 | 0.56 | ≥0.5 |
| Wet on-slip | ASTM-1677 | 0.32 | 0.35 | 0.33 | ≥0.3 |
| Permanent high compression is askew | VF-B10 | 39 | 36 | 29 | 45-60 |
Vertically bounce-back reaches 50-60% to sole prepared by the material that the present invention is provided, far above general midsole bounce-back (20-
35)；Proportion 0.38-0.6, weight is General Purpose Rubber bottom (rubber-sole proportion 1.1-1.2) 30-40%；The wear-resisting 80-150 of DIN,
Reach the wear-resisting requirement of rubber-sole；Dry/wet on-slip >=0.5/0.3, it is similar with rubber sliding-proof effect；Permanent high compression is askew to be less than 40.
One embodiment of the invention is the foregoing is only, the present invention, all use equivalent substitutions or equivalent transformation is not intended to limit
The technical scheme that is obtained of mode, all fall within protection scope of the present invention.
Claims (9)
1. a kind of RPUC high-performance moldeds material for sole of shoe, it is characterised in that：Its formula is as follows：
100 parts of sizing material
0.6-1 parts of bridging agent
5.2-10.8 parts of auxiliary agent
2-5 parts of colorant.
2. a kind of RPUI high-performance according to claim 1 projects material for sole of shoe, it is characterised in that the sizing material includes three
First EP rubbers and elastic composite, the ethylene propylene diene rubber use EPDM3722, and the elastic composite is adopted
With N502 and Infuse 9507.
3. a kind of RPUI high-performance according to claim 2 projects material for sole of shoe, it is characterised in that the formula of the sizing material
It is as follows：20-50 parts of ethylene propylene diene rubber, 10-30 parts of N502 elastic composites, the elastic composites of Infuse 9507
30-50 parts.
4. a kind of RPUI high-performance according to claim 1 projects material for sole of shoe, it is characterised in that the bridging agent is used
The tasteless peroxide of environment-friendly type, the peroxide includes but is not limited to Arkema Luperox F flakes's or AKZO
14S-FC。
5. a kind of RPUI high-performance according to claim 1 projects material for sole of shoe, it is characterised in that the auxiliary agent includes resistance to
Grinding agent, stearic acid, alkaline oxygenated zinc and foaming agent, the auxiliary formula are as follows：2-5 parts of anti-wear agent, 0.4-0.8 parts of stearic acid,
Alkaline oxygenated zinc 0.8-2 parts, 2-3 parts of foaming agent.
6. a kind of RPUI high-performance according to claim 5 projects material for sole of shoe, it is characterised in that the anti-wear agent is used
DIN150, the stearic acid uses ST1801, and the alkaline oxygenated zinc uses ZINC, and the foaming agent uses middle temperature foaming agent,
The middle temperature foaming agent includes but is not limited to South Korea brocade ocean JTR-TL or Lin Gebei HH808B.
7. a kind of RPUI high-performance according to claim 1 projects material for sole of shoe, it is characterised in that its preparation process is such as
Under：
Step 1, raw material is weighed according to formula；
Step 2, banbury (also known as profit takes machine) is warming up to 70-80 DEG C, adds micelle and carry out mastication, be continuously heating to 90-100
DEG C, add anti-wear agent, stearic acid, alkaline oxygenated zinc, colorant and kneaded；
Step 3, be warming up to 115-120 DEG C, carry out weight mixing, be naturally cooling to 100-105 DEG C during mixing, input foaming agent with
Bridging agent, continues to knead discharging after 3min, while controlling temperature to be less than 110 DEG C；
Step 4, the kneading material unloaded is put into comminutor and granulated, obtain pellet；
Step 5, the different big small powder of expansion ratio is prepared according to above-mentioned steps, the formulation differences of the small powder and aniseed are in foaming
Agent ratio is 2: 3；
Step 6, aniseed and small powder are loaded into hot pressing ejaculator charging basket after expansion ratio ratio is uniformly mixed with batch mixer on demand,
Rifle is penetrated by ejaculator again and injects mould molding, described to penetrate rifle wise temperature parameter as follows：92 DEG C of first paragraph, 92 DEG C of second segment,
3rd section 94 DEG C, the 4th section 94 DEG C；
Step 7, it is put into constant temperature oven after shooting foaming semi-finished product are taken out and makees stable dimensions sizing, constant temperature steadiness parameter：175
℃*500S；
Step 8, constant temperature oven dried after carry out cooling and shaping, cooling condition be 5 DEG C * 5 minutes；
Step 9, repaiied after cooling and shaping except sole flash, you can obtain product shoes bottom.
8. a kind of RPUI high-performance according to claim 7 projects material for sole of shoe, it is characterised in that in the step 4
Granulation conditions are as follows：Set 70 ± 5 DEG C of die head temperature；30 ± 5 DEG C of first paragraph temperature；30 ± 5 DEG C of second segment temperature；3rd section of temperature
30 ± 5 DEG C of degree；Set main frame speed 28；Mixer speed 19；Die head motor speed 11 ± 1.
9. a kind of RPUI high-performance according to claim 7 projects material for sole of shoe, it is characterised in that in the step 7
The baking oven time is spent for 40min, using five sections of baking ovens, the oven temperature is respectively 75 DEG C/70 DEG C/65 DEG C/60 DEG C/55 DEG C.
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| CN201710149875.1A CN107099162A (en) | 2017-03-14 | 2017-03-14 | A kind of RPUI high-performance projects material for sole of shoe |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710149875.1A CN107099162A (en) | 2017-03-14 | 2017-03-14 | A kind of RPUI high-performance projects material for sole of shoe |
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2017
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| CN105670052A (en) * | 2016-04-18 | 2016-06-15 | 晋江新绮达鞋材有限责任公司 | Novel high-resilience foamable rubber shoe sole material and preparation method thereof |
| CN105968439A (en) * | 2016-07-20 | 2016-09-28 | 南京东亚橡塑制品有限公司 | Preparation method of oil-resistant antiskid rain boot sole material |
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